NL2022836B1 - Method for preparing ultralow-temperature high-capacity supercapacitor and use thereof - Google Patents

Method for preparing ultralow-temperature high-capacity supercapacitor and use thereof Download PDF

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NL2022836B1
NL2022836B1 NL2022836A NL2022836A NL2022836B1 NL 2022836 B1 NL2022836 B1 NL 2022836B1 NL 2022836 A NL2022836 A NL 2022836A NL 2022836 A NL2022836 A NL 2022836A NL 2022836 B1 NL2022836 B1 NL 2022836B1
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supercapacitor
super capacitor
carbon material
porous carbon
low temperature
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NL2022836A
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Dutch (nl)
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Ding Jianning
Yuan Ningyi
Xu Jiang
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Univ Jiangsu
Univ Changzhou
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/38—Carbon pastes or blends; Binders or additives therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/60—Liquid electrolytes characterised by the solvent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes

Abstract

The present invention provides a method for preparing an ultralow—temperature high—capacity supercapacitor. The electrode material used is a composite porous carbon material having micropores and mesopores, and having a specific surface area greater than 2500 mZ/g, Where the pore size of the micropore is larger than 0.8 nm, the pore size of the mesopore is from 2 to 3.0 nm, and the micropores account for above 70%. The electrolytic solution for the supercapacitor is a mixed solvent of l, 3—dioxolane (or methyl formate MF, or a mixture of the two) and acetonitrile, and spiro quaternary ammonium tetrafluoroborate SBP—BF4 is dissolved. The supercapacitor prepared based on the electrode material in combination With the electrolytic solution has a mass specific capacitance greater than 150 F/g and a volume specific capacitance greater than 80 F/cm3 at —lOO°C and a current density larger than 1 A/g.

Description

METHOD FOR PREPARING ULTRALOW-TEMPERATURE HIGH-CAPACITY SUPERCAPACITOR AND USE THEREOF
FIELD OF THE INVENTION
The present invention relates to the field of supercapacitor technologies, and more particularly to a method for preparing a supercapacitor having superior performance in an ultralow-temperature environment.
DESCRIPTION OF THE RELATED ART
Higher requirements are put forward for energy storage devices in low-temperature working environments, such as high-altitude regions, extremely cold areas, and in aerospace and other fields. In general, lithium ion batteries have high energy storage capabilities. However, the reduction in working temperature severely decreases the conductivity of electrolytes, greatly increases the resistance of ions passing through a solid electrolyte interface, and limits the operating temperature of the lithium ion battery. Usually, the minimum temperature at which lithium ions can work normally is -20°C (3, 4). Compared to lithium ion batteries, supercapacitors are still limited although the operating temperature is somewhat reduced. By using the conventional solvents, such as acetonitrile (ACN) or propylene carbonate (PC), the operating temperatures can be as low as -45°C and -25°C, respectively. Modification of the electrolytic solution (for example, by a mixed solvent, or by adding different salts to the solvent) mainly serves to reduce the freezing point of the solvent, thereby alleviating a sharp drop in conductivity due to decreased temperature. For example, a capacitor with a mixed solvent of ACN/1,3-dioxane (DIOX) (1:1) can operate at a temperate as low as -70°C compared to a capacitor with pure ACN solvent. Even so, at lower temperatures, the capacitance and rate performance of the capacitor are still much lower than those at room temperature. For carbon materials, although carbon nanotubes or carbon onions, as active materials, can greatly improve the performance of supercapacitors at low temperatures; however, the mass and volume specific capacitances are too low to be used for commercial purposes.
SUMMARY OF THE INVENTION
The technical problem to be solved by the present invention is to overcome the technical difficulty that the supercapacitor in the prior art has poor charge and discharge performance in an ultralow-temperature environment.
For the above purpose, the invention provides the following technical solutions.
In one aspect, the invention provides an ultralow-temperature high-capacity supercapacitor, which comprises a composite porous carbon material having micropores and mesopores as an electrode material, and spiro quaternary ammonium tetrafluoroborate (SBP-BF4) dissolved in a mixed solvent as an electrolytic solution. The composite porous carbon material has a specific surface area greater than 2500 m2/g, the pore size of the micropore is larger than 0.8 nm, the pore size of the mesopore is 2-3.0 nm, and the micropores account for above 70%. The supercapacitor has a mass specific capacitance greater than 150 F/g and a volume specific capacitance greater than 80 F/cm3 at -100°C and a current density greater than 1 A/g.
The porous carbon material is prepared by a process comprising the following steps:
placing dried biomass carbon in a tube furnace, and performing rapid carbonization in the presence of argon by heating to 400-500°C at a ramping rate greater than or equal to 100°C/min and maintaining at this temperature for half an hour;
cooling the tube furnace to room temperature to remove the carbonized product, and mixing the carbonized product with potassium hydroxide and grinding for 20 min in a mortar such that the carbon material is uniformly mixed with potassium hydroxide, wherein the weight ratio of the carbonized product to KOH is 1:3;
placing the mixed material in a tube furnace and activating at 800°C in the presence of argon, and cooling the tube furnace to room temperature; and removing and washing the activated product with hydrochloric acid, and washing with water until neutral to obtain a composite porous carbon material.
The mixed solvent is a mixture of 1, 3-dioxolane and acetonitrile, or a mixture of methyl formate and acetonitrile, or a mixture of 1, 3-dioxolane, methyl formate and acetonitrile, wherein the volume ratio of 1, 3-dioxolane, methyl formate, or 1, 3-dioxolane and methyl formate to acetonitrile is greater than 2.
The specific size of the micropores eliminates the limitation in removal of solvent from the solvated ions at low temperatures, and the specific size of the mesopores ensures a fast transport path for ions in the porous carbon. The ratio of micropores to mesopores and the specific surface area of the porous carbon guarantee the high capacity of the capacitor, while also taking into account the transport of ions in the electrolytic solution and the equilibrium of the rate of ion adsorption on the surface of the porous carbon. A high performance supercapacitor operating at -100°C is achieved by using spiro quaternary ammonium tetrafluoroborate (SBP-BF4) dissolved in the mixed solvent as an electrolytic solution.
In another aspect, the present invention also provides a method for preparing an ultralow-temperature high-capacity supercapacitor, which comprises specifically the following steps:
(A) preparation of electrode sheet for supercapacitor: mixing and grinding the composite porous carbon material with a conductive agent and a binder for 20 min in a mortar such that the materials are uniformly mixed; adding a suitable amount of solvent to continuously grind to ensure that the slurry is mixed uniformly, and the slurry is able to be coated without self-casting, and coating the slurry on a carbon coated aluminum foil by a doctor blade to form an electrode sheet;
(B) formulation of electrolytic solution: dissolving SBP-BF4 in a mixed solvent which is a mixture of 1, 3-dioxolane and acetonitrile, or a mixture of methyl formate and acetonitrile, or a mixture of 1,3-dioxolane, methyl formate and acetonitrile, to form an electrolytic solution, wherein the volume ratio of 1, 3-dioxolane, methyl formate, or 1, 3-dioxolane and methyl formate to acetonitrile is greater than 2, and the concentration of SBP-BF4 is 0.2 - 0.5 mol/L; and (C) assembly of supercapacitor: drying and transferring the electrode sheet quickly to a glove box, assembling a CR2025 button cell, and after the cell is assembled standing the cell for formation for use in subsequent test.
In a preferred embodiment of the present invention, in the step (1), the conductive agent is Super-P, the binder is CMC, and the solvent is deionized water, in which the weight ratio of the composite porous carbon material, the conductive agent, and the binder is 8-23:1:1.
In a preferred embodiment of the present invention, in the step (3), the electrode sheet is dried for 12 hr in a vacuum oven at 120°C. After the cell is assembled, the formation time is 12 hr.
Performance test of supercapacitor: The supercapacitor obtained in step (3) is subjected to a charge and discharge test at a low temperature.
In still another aspect, the present invention further provides use of the ultralow-temperature high-capacity supercapacitor in high-altitude regions, deep sea, aerospace and military fields. The supercapacitor assembled based on the composite porous carbon material in combination with the novel electrolytic solution has excellent electrochemical performance under ultralow-temperature conditions such as in high-altitude regions, deep sea, and in aviation, aerospace and military fields, thereby solving the energy storage problem under ultralow-temperature conditions.
As compared with the prior art, the invention has the following beneficial effects:
(1) The supercapacitor is a new type of energy storage device that is environmentally friendly by comparison to fossil fuels.
(2) The carbon material is abundant in source and low in price, and the assembly of supercapacitor is simple, and this can meet the needs of industrial production.
(3) The supercapacitor has excellent charge and discharge performance under ultralow-temperature conditions, thus solving the energy storage problem under extreme conditions.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 is a cyclic voltammetry curve at various temperatures of a capacitor produced in embodiment 1.
Fig. 2 is a cyclic voltammetry curve at different temperatures of a capacitor produced in comparative embodiment 1.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The invention will be further illustrated in more detail with reference to the accompanying drawings and embodiments. It is noted that, the following embodiments only are intended for purposes of illustration, but are not intended to limit the scope of the present invention.
An embodiment or embodiments as used herein refers to a particular feature, structure, or characteristic that can be included in at least one implementation of the invention. The expressions of in one embodiment in different parts of the specification do not refer to the same embodiments, nor represent separate or selective embodiments mutually exclusive to other embodiments.
The present invention provides a method for preparing an ultralow-temperature high-capacity supercapacitor, which comprises the following steps.
Step 1: Preparation of electrode sheet for supercapacitor: a carbon material is mixed and ground with a conductive agent and a binder for 20 min in a mortar until the materials are uniformly mixed, a suitable amount of solvent is added to continuously grind to ensure that the slurry is mixed uniformly, and the slurry is able to be coated without self-casting. The slurry is coated on a carbon coated aluminum foil by a doctor blade to form an electrode sheet.
Specifically, the carbon material used is a composite porous carbon material having micropores and mesopores, and having a specific surface area greater than 2500 m2/g, where the pore size of the micropore is larger than 0.8 nm, the pore size of the mesopore is from 2 to 3.0 nm, and the micropores account for above 70%. The conductive agent is Super-P, the binder is CMC, and the solvent is deionized water.
Step 2: Formulation of electrolytic solution: SBP-BF4 is dissolved in a mixed solvent of 1,3-dioxolane (or MF, or a mixture of the two) with acetonitrile to form an electrolytic solution.
Specifically, the volume ratio of 1,3-dioxolane (or MF, or a mixture of the two) to acetonitrile in the mixed solvent is greater than 2. The concentration of SBP-BF4 is 0.2-0.5 mol/L.
Step 3: Assembly of supercapacitor: The electrode sheet is dried and transferred quickly to a glove box, and a CR2025 button cell is assembled. After the cell is assembled, the cell is stood for formation for use in subsequent test. Specifically, the electrode sheet is dried for 12 hr in a vacuum oven at 120°C. After the cell is assembled, the formation time is 12 hr.
Step 4: Performance test of supercapacitor: The supercapacitor obtained in the step 3 is subjected to a charge and discharge test at a low temperature.
Hereinafter three embodiments which fully embody the contents of the invention are described in more detail in combination with the preparation method of an ultralow-temperature high-capacity supercapacitor.
Embodiment 1
Preparation of composite porous carbon
Dried biomass carbon was placed in a tube furnace in the presence of argon, heated to 400°C at a ramping rate of 100°C/min and maintained at this temperature for half an hour for rapid carbonization. The tube furnace was cooled to room temperature, and the carbonized product was removed, mixed with potassium hydroxide, ground for 20 min in a mortar until the carbon material was uniformly mixed with potassium hydroxide. The mixed material z
was placed in a tube furnace and activated at 800°C in the presence of argon. The tube furnace was cooled to room temperature; the activated product was removed, and washed with hydrochloric acid, and then with water until neutral to obtain a composite porous carbon, where the weight ratio of the carbonized product to KOH was 1:3.
Preparation of supercapacitor
Step 1 : Preparation of electrode sheet for supercapacitor: The prepared porous carbon material was mixed with the conductive agent Super-P and the binder CMC at a ratio of 92:4:4 for 20 min in a mortar until the materials were uniformly mixed, wherein the porous carbon material has a specific surface area greater than 2500 m2/g, and has micropores with a pore size larger than 0.8 nm and mesopores with a pore size of 2-3.Onm, and the micropores account for above 70%. A suitable amount of deionized water was added to continuously grind to ensure that the slurry was mixed uniformly, and the slurry was able to be coated without self-casting. The slurry was coated on a carbon coated aluminum foil by a doctor blade to form an electrode sheet.
Step 2: Formulation of electrolytic solution: The solvent was a mixed solvent of 1,3-dioxolane and acetonitrile at a volume ratio of 3:1, and SBP-BF4 was dissolved at a concentration of 0.2 mol/L.
Step 3: Assembly of supercapacitor: The electrode sheet was dried for 12 hr in a vacuum oven at 120°C and then transferred quickly to a glove box, and a CR2025 button cell was assembled. After the cell was assembled, the cell was stood for 12h for formation for use in subsequent test.
Step 4: Performance test of supercapacitor: Charge and discharge performance test of the supercapacitor obtained in Step 3 was carried out at -100°C and a current density of 1.5 A/g, and the mass and volume specific capacitance of the supercapacitor were calculated.
The supercapacitor prepared based on the electrode material in combination with the novel electrolytic solution has a mass specific capacitance greater than 150 F/g and a volume specific capacitance greater than 80 F/cm3 at -100°C and a current density larger than 1 A/g.
Fig. 1 is a cyclic voltammetry curve at various temperatures of a capacitor prepared in embodiment 1; and Fig. 2 is a cyclic voltammetry curve at different temperatures of a capacitor prepared in comparative embodiment 1.
As can be seen from the figures, in embodiment 1, the capacitance value of the system changes slightly with the decrease of temperature. However, in comparative embodiment 1, the capacitance value declines drastically as the temperature decreases.
Embodiment 2
The preparation of composite porous carbon was the same as that in Embodiment 1.
Preparation of supercapacitor
Step 1: Preparation of electrode sheet for supercapacitor: A porous carbon material was mixed and ground with the conductive agent Super-P and the binder CMC at a ratio of 90:5:5 for 20 min in a mortar until the materials were uniformly mixed, wherein the porous carbon material has a specific surface area greater than 2500 m2/g, and has micropores with a pore size larger than 0.8 nm and mesopores with a pore size of 2-3.0 nm, and the micropores account for above 70%. A suitable amount of deionized water was added to continuously grind to ensure that the slurry was mixed uniformly, and the slurry was able to be coated without self-casting. The slurry was coated on a carbon coated aluminum foil by a doctor blade to form an electrode sheet.
Step 2: Formulation of electrolytic solution: The solvent was a mixed solvent of MF and acetonitrile at a volume ratio of 3:1, and SBP-BF4 was dissolved at a concentration of 0.3 mol/L.
Step 3: Assembly of supercapacitor: The electrode sheet was dried for 12 hr in a vacuum oven at 120°C and then transferred quickly to a glove box, and a CR2025 button cell was assembled. After the cell was assembled, the cell was stood for 12h for formation for use in subsequent test.
Step 4: Performance test of supercapacitor: charge and discharge performance test of the supercapacitor obtained in step 3 was carried out at
-100°C and a current density of 2 A/g, and the mass and volume specific capacitance of the supercapacitor were calculated.
The supercapacitor prepared based on the electrode material in combination with the novel electrolytic solution has a mass specific capacitance greater than 150 F/g and a volume specific capacitance greater than 80 F/cm3 at -100°C and a current density larger than 1 A/g.
Embodiment 3
The preparation of composite porous carbon was the same as that in Embodiment 1.
Preparation of supercapacitor
Step 1: Preparation of electrode sheet for supercapacitor: A porous carbon material was mixed and ground with the conductive agent Super-P and the binder CMC at a ratio of 8:1:1 for 20 min in a mortar until the materials were uniformly mixed, wherein the porous carbon material has a specific surface area greater than 2500 m2/g, and has micropores with a pore size larger than 0.8 nm and mesopores with a pore size of 2-3.0 nm, and the micropores account for above 70%. A suitable amount of deionized water was added to continuously grind to ensure that the slurry was mixed uniformly, and the slurry was able to be coated without self-casting. The slurry was coated on a carbon coated aluminum foil by a doctor blade to form an electrode sheet.
Step 2: Formulation of electrolytic solution: A mixed solution of 1,3-dioxolane and MF (1:1) was prepared, which was then mixed with acetonitrile at a volume ratio of 3:1 to form a mixed solvent. SBP-BF4 was dissolved at a concentration of 0.5 mol/L.
Step 3: Assembly of supercapacitor: The electrode sheet was dried for 12 hr in a vacuum oven at 120°C and then transferred quickly to a glove box, and a CR2025 button cell was assembled. After the cell was assembled, the cell was stood for 12h for formation for use in subsequent test.
Step 4: Performance test of supercapacitor: charge and discharge performance test of the supercapacitor obtained in step 3 was carried out at -100°C and a current density of 2 A/g, and the mass and volume specific capacitance of the supercapacitor were calculated.
The supercapacitor prepared based on the electrode material in combination with the novel electrolytic solution has a mass specific capacitance greater than 150 F/g and a volume specific capacitance greater than 80 F/cm3 at -100°C and a current density larger than 1 A/g.
Comparative Embodiment 1
Preparation of supercapacitor
Step 1: Preparation of electrode sheet for supercapacitor: A commercially available carbon material is mixed and ground with a conductive agent Super-P and a binder CMC at a ratio of 92:4:4 for 20 min in a mortar until the materials are uniformly mixed, a suitable amount of solvent was added to continuously grind to ensure that the slurry was mixed uniformly, and the slurry was able to be coated without self-casting. The slurry was coated on a carbon coated aluminum foil by a doctor blade to form an electrode sheet.
The other steps were the same as those in embodiment 1.
The supercapacitor prepared based on the above electrode material in combination with the novel electrolytic solution has a mass specific capacitance greater than 85 F/g and a volume specific capacitance greater than 47 F/cm3 at -100°C and a current density larger than 1 A/g.
An ordinary carbon material has a large number of micropores of which the pore diameter is less than 0.8 nm. When such a carbon material is used as an electrode material, the performance is affected by desolvation of ions under low temperature conditions. The lower the temperature is, the more difficult the desolvation and the worse the performance will be.
Comparative Embodiment 2
Preparation of supercapacitor
Step 2: Formulation of electrolytic solution: The solvent was 1,3-dioxolane or MF, and SBP-BF4 was dissolved at a concentration of SBP-BF4 0.2 mol/L.
The other steps were the same as those in Embodiment 1.
The supercapacitor prepared based on the above electrode material in
1 combination with the electrolytic solution has a mass specific capacitance greater than 135 F/g and a volume specific capacitance greater than 71 F/cm3 at -100°C and a current density larger than 1 A/g.
Since 1,3-dioxolane or MF has a large viscosity, when one of them is used alone, the viscosity of the electrolytic solution is increased and the low-temperature performance is degraded.
Comparative Embodiment 3
Step 2: Formulation of electrolytic solution: The solvent was ACN, and SBP-BF4 was dissol ved at a concentration of 0.2 mol/L.
The other steps were the same as those in Embodiment 1.
The supercapacitor prepared based on the above electrode material in combination with the electrolytic solution has a mass specific capacitance greater than 0 F/g and a volume specific capacitance greater than 0 F/cm3 at -100°C and a current density larger than 1 A/g.
When used as a single solvent, ACN has a freezing point of -45°C. At a temperature below -45°C, the electrolytic solution is gradually solidified, so normal charge and discharge cannot be achieved.
Comparative Embodiment 4
Preparation of supercapacitor
Step 2: Formulation of electrolytic solution: The solvent was propylene carbonate, and SBP-BF4 was dissolved at a concentration of 0.2 mol/L.
The other steps were the same as those in embodiment 1.
The supercapacitor prepared based on the above electrode material in combination with the electrolytic solution has a mass specific capacitance greater than 0 F/g and a volume specific capacitance greater than 0 F/cm3 at -100°C and a current density larger than 1 A/g.
In case that propylene carbonate (PC) is used as a solvent to dissolve the electrolyte, the conductivity, viscosity and dielectric constant are not as good as those when ACN is used, and the operating temperature is not lower than -40°C, so the performance is poor at lower temperatures.
One of ordinary skill in the art will appreciate that one of the features or objects of the present invention is in that: the method for producing the ultralow-temperature high-capacity supercapacitor has the advantages that (1) the supercapacitor is a new type of energy storage device that is environmentally friendly compared to fossil fuels; (2) the carbon material is 5 abundant in source and low in price, and the assembly of supercapacitor is simple, and this can meet the needs of industrial production; and (3) the supercapacitor has excellent charge and discharge performance under ultralow-temperature conditions, thus solving the energy storage problem under extreme conditions.
The above description is only preferred embodiments of the present invention and not intended to limit the present invention, it should be noted that those of ordinary skill in the art can further make various modifications and variations without departing from the technical principles of the present invention, and these modifications and variations also should be considered to 15 be within the scope of protection of the present invention.

Claims (8)

ConclusiesConclusions 1. Ultra-lagetemperatuur en hogecapaciteit supercondensator, omvattende een composiet poreus koolsfofmateriaal met microporiën en mesoporiën als een electrodemateriaal, en sprio quarternair ammoniumtetrafluorboraat (SBP-BF4) opgelost in een gemengd oplosmiddel as als een elektrolytische oplossing waarin het composiet poreus koolstofmateriaal een specifiek oppervlak heeft groter dan 2500 m2/g, de poriegrootte van de microporie groter is dan 0,8 nm, de poriegrootte van de mesoporie 2 - 3,0 nm is, waarbij de microporiën meer dan 70% uitmaken, en de supercondensator een massa-specifieke capaciteit heeft groter dan 150F/g en een volume-specifieke capaciteit heeft groter dan 80 F/cm3 en een stroomdichtheid groter dan 1 A/g.An ultra low temperature and high capacity super capacitor, comprising a composite porous carbon material with micropores and mesopores as an electrode material, and sprio quaternary ammonium tetrafluoroborate (SBP-BF4) dissolved in a mixed solvent ash as an electrolytic solution in which the composite porous carbon material has a specific surface greater than 2500 m2 / g, the pore size of the micropore is greater than 0.8 nm, the pore size of the mesopore is 2 - 3.0 nm, the micropores making up more than 70%, and the super capacitor having a mass-specific capacity has greater than 150 F / g and a volume specific capacity has greater than 80 F / cm3 and a current density greater than 1 A / g. 2. Ultra-lagetemperatuur en hogecapaciteit supercondensator volgens conclusie 1, waarbij het composiet poreus koolstofmateriaal is vervaardigd volgens de stappen van:The ultra low temperature and high capacity super capacitor of claim 1, wherein the composite porous carbon material is made according to the steps of: het plaatsen van gedroogde biomassa-koolstof in een buisoven, en het uitvoeren van een snelle carbonisatie in de aanwezigheid van argon door verhitting tot 400-500°C bij een warmtetoename groter dan of gelijk aan 100°C/min, en het handhaven van de temperatuur gedurende een half uur;placing dried biomass-carbon in a tube furnace, and performing rapid carbonization in the presence of argon by heating to 400-500 ° C at a heat increase greater than or equal to 100 ° C / min, and maintaining the temperature for half an hour; het koelen van de buisoven tot kamertemperatuur teneinde het gecarboniseerde product te verwijderen, en het mengen van het gecarboniseerde product met kaliumhydroxide en het vermalen ervan in een mortier, zodat het koolstofmateriaal uniform is gemengd met kaliumhydroxide, waarbij de gewichtsverhouding tussen gecarboniseerd product en kaliumhydroxide 1:3 is;cooling the tube furnace to room temperature to remove the carbonized product, and mixing the carbonized product with potassium hydroxide and grinding it into a mortar so that the carbon material is uniformly mixed with potassium hydroxide, the weight ratio between carbonized product and potassium hydroxide 1: 3; het plaatsen van het gemengde materiaal in een buisoven en het activeren ervan bij 800°C in de aanwezigheid van argon, en het koelen van de buisoven tot kamertemperatuur, en het verwijderen en wassen van het geactiveerde product met zoutzuur, en het wassen met water tot een neutrale pH-waarde, teninde een composiet poreus koolstofmateriaal te verkrijgen.placing the mixed material in a tube furnace and activating it at 800 ° C in the presence of argon, and cooling the tube furnace to room temperature, and removing and washing the activated product with hydrochloric acid, and washing with water until a neutral pH value, in order to obtain a composite porous carbon material. 3. Ultra-lagetemperatuur en hogecapaciteit supercondensator volgens conclusie 1, waarbij het gemengde oplosmiddel een mengsel is van 1,3-dioxolaan en acetonitril, or een mengsel van methylformaat en acetonitril, of een mengsel van 1,3-dioxolaan, methylformaat en acetonitril waarbij de volumeverhouding tussen enerzijds 1,3dioxolaan, resp. methylformaat, resp. 1,3-dioxolaan en methylformaat, en anderzijds acetonitiril groter is dan 2.The ultra low temperature and high capacity super capacitor according to claim 1, wherein the mixed solvent is a mixture of 1,3-dioxolane and acetonitrile, or a mixture of methyl format and acetonitrile, or a mixture of 1,3-dioxolane, methyl format and acetonitrile wherein the volume ratio between 1.3 dioxolane and resp. methyl format, resp. 1,3-dioxolane and methyl format, and on the other hand acetonitiril is greater than 2. 4. Werkwijze voor het vervaardigen van een ultra-lagetemperatuur en hogecapaciteit supercondensator volgens conclusie 1, omvattende de stappen van:The method for manufacturing an ultra low temperature and high capacity super capacitor according to claim 1, comprising the steps of: (A) het vervaardigen van een elektrodelaag voor de supercondensator: het mengen en vermalen van het composiet poreus koolstofmateriaal met een geleider en een bindmiddel gedurende 20 min in een mortier zodat de stoffen uniform worden gemengd; het toevoegen van een oplosmiddel om voor het continu vermalen teneinde te verzekeren dat de slurrie uniform wordt gemengd, en de slurrie geschikt is als bekledingsmiddel zonder gietproces; en het met een rakel aanbrengen van de slurrie op een koolstofbeklede aluminiumfolie om een elektrodelaag te vormen;(A) producing an electrode layer for the super capacitor: mixing and grinding the composite porous carbon material with a conductor and a binder for 20 minutes in a mortar so that the substances are uniformly mixed; adding a solvent for continuous milling to ensure that the slurry is uniformly mixed, and the slurry is suitable as a coating agent without casting process; and doctoring the slurry on a carbon-coated aluminum foil to form an electrode layer; (B) het formuleren van een elektrolytische oplossing door het oplossen van SBP-BF4 in een gemengd oplosmiddel; en (C) het assembleren van een supercondensator door het drogen en snel overbrengen van de elektrodelaag naar een glove box; het assembleren van een CR2025 knoopvormige cel, en het verschaffen van de cel na assemblage voor onderwerping aan een opvolgende test.(B) formulating an electrolytic solution by dissolving SBP-BF4 in a mixed solvent; and (C) assembling a super capacitor by drying and quickly transferring the electrode layer to a glove box; assembling a CR2025 button-shaped cell, and providing the cell after assembly for submission to a subsequent test. 5. Werkwijze voor het vervaardigen van een ultra-lagetemperatuur en hogecapaciteit supercondensator volgens conclusie 4, waarbij in stap (1) de geleider is Super-P, het bindmiddel is CMC, en het oplosmiddel is gedeïoniseerd water, en de gewichtsverhouding tussen het composiet poreus koolstofmateriaal, de geleider SuperP, en het bindmiddel CMC 8-23 : 1 : 1 bedraagt.The method for manufacturing an ultra low temperature and high capacity super capacitor according to claim 4, wherein in step (1) the conductor is Super-P, the binder is CMC, and the solvent is deionized water, and the weight ratio between the composite porous carbon material, the SuperP conductor, and the CMC binder is 8-23: 1: 1. 6. Werkwijze voor het vervaardigen van een ultra-lagetemperatuur en hogecapaciteit supercondensator volgens conclusie 4, waarbij in stap (2) de concentratie van SBP-BF4 is 0,2-0,5 mol/1.The method for manufacturing an ultra low temperature and high capacity super capacitor according to claim 4, wherein in step (2) the concentration of SBP-BF4 is 0.2-0.5 mol / l. 7. Werkwijze voor het vervaardigen van een ultra-lagetemperatnur en hogecapaciteit supercondensator volgens conclusie 4, waarbij in stap (3) de elektrodelaag is gedroogd in een vacuümoven bij 120°C gedurende 12 uur, en de formeringstijd 12 uur na assemblage bedraagt.The method for manufacturing an ultra low temperature and high capacity super capacitor according to claim 4, wherein in step (3) the electrode layer is dried in a vacuum oven at 120 ° C for 12 hours, and the forming time is 12 hours after assembly. 8. Toepassing van een ultra-lagetemperatuur en hogecapaciteit supercondensator volgens conclusie 1 in hoog-gelegen regio's, diepzee, ruimtevaart, en militaire gebieden.The use of an ultra-low temperature and high-capacity super capacitor according to claim 1 in high-lying regions, deep-sea, space travel, and military areas.
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